Gordon Fraser, 48, acting Deputy Chief Constable of Leicestershire Police, is due to appear before magistrates in St Albans with wife Teresa, 42, on Friday.
It is alleged that Mrs Fraser accepted responsibility for a speeding offence committed by her husband on September 29 last year in Scotland, prosecutors said.
The case was investigated by Hertfordshire Constabulary due to Fraser's links to the Leicestershire force.
Baljit Ubhey, chief crown prosecutor for Thames and Chiltern Crown Prosecution Service, said: "A criminal complaint was made alleging that Mrs Fraser had accepted responsibility for a speeding offence allegedly committed by Mr Fraser on 29 September 2011 in Strathclyde.
"Having carefully considered all of the available evidence, we concluded that there is sufficient evidence to bring criminal charges against Mr and Mrs Fraser and therefore, authorised Hertfordshire Constabulary to charge them with doing acts tending to pervert the course of justice.
"The essence of the charge is that Mr Fraser, having allegedly committed a speeding offence, falsely informed the investigating authorities that Mrs Fraser had been the driver of the vehicle in question, and she falsely accepted responsibility for the speeding offence.
"The decision to charge was taken in accordance with the Code for Crown Prosecutors."
It is a similar allegation to that faced by Chris Huhne and his former wife Vicky Pryce. They have also each been charged with perverting the course of justice, over the allegation that Mr Huhne persuaded his then spouse to take penalty points for a speeding offence in 2003.
Gordon Fraser joined the Leicestershire force in June 2009 and was made temporary chief constable six months later.
He previously served with West Midlands police, where he fulfilled roles such as Head of Intelligence, Head of Crime and Head of Business and Service Improvement.
Fraser won a national award for his work dismantling serious and organised crime networks.